Ligand-controlled product selectivity in gold-catalyzed double cycloisomerization of 1,11-Dien-3,9-Diyne benzoates

A synthetic method to prepare tricyclic bridged heptenones and hexenones from gold(I)-catalyzed double cycloisomerization of 1,11-dien-3,9-diyne benzoates is described. A divergence in product selectivity was achieved by fine-tuning the steric nature of the ligand of the Au(I) catalyst. In the presence of [MeCNAu(JohnPhos)]+SbF6– (JohnPhos = (1,1′-biphenyl-2-yl)-di-tert-butylphosphine) as the catalyst, tandem 1,3-acyloxy migration/metallo-Nazarov cyclization/1,6-enyne addition/Cope rearrangement of the substrate was found to selectively occur to afford the bridged heptenone adduct. In contrast, changing the Au(I) catalyst to [MeCNAu(Me4tBuXPhos)]+SbF6– (Me4tBuXPhos = di-tert-butyl(2′,4′,6′-triisopropyl-3,4,5,6-tetramethyl-[1,1′-biphenyl]-2-yl)phosphine) was observed to result in the 1,11-dien-3,9-diyne benzoate undergoing a more rapid tandem 1,3-acyloxy migration/metallo-Nazarov cyclization/[4 + 2]-cyclization pathway to give the bridged hexenone derivative

Gold-catalyzed dehydrogenative cycloisomerization of 1,4-Enyne Esters to 3,5-Disubstituted Phenol derivatives

A method to prepare synthetically important 3,5-disubstituted phenol derivatives that relies on the sequential gold(I)-catalyzed dehydrogenative cycloisomerization of 1,4-enyne esters in the presence of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) or N-fluorobenzenesulfonimide (NFSI) is described. The synthetic versatility of the methodology was exemplified by a gram-scale reaction of one example, the ease to realize subsequent functional transformations of an adduct, and the application of the method to the synthesis of the bioactive molecule LUF5771

Gold-catalyzed cycloisomerization and Diels-Alder reaction of 1,4,9-Dienyne Esters to 3 a,6-Methanoisoindole Esters with pro-inflammatory cytokine antagonist activity

A synthetic method to prepare 3a,6-methanoisoindole esters efficiently by gold(I)-catalyzed tandem 1,2-acyloxy migration/Nazarov cyclization followed by Diels–Alder reaction of 1,4,9-dienyne esters is described. We also report the ability of one example to inhibit binding of tumor necrosis factor-α (TNF-α) to the tumor necrosis factor receptor 1 (TNFR1) site and TNF-α-induced nuclear factor κ-light-chain-enhancer of activated B cells (NF-κB) activation in cell at a half-maximal inhibitory concentration (IC50) value of 6.6 μM. Along with this is a study showing the isoindolyl derivative to exhibit low toxicity toward human hepatocellular liver carcinoma (HepG2) cells and its possible mode of activity based on molecular modeling analysis

CA-SSL: Class-Agnostic Semi-Supervised Learning for Detection and Segmentation

To improve instance-level detection/segmentation performance, existing self-supervised and semi-supervised methods extract either task-unrelated or task-specific training signals from unlabeled data. We show that these two approaches, at the two extreme ends of the task-specificity spectrum, are suboptimal for the task performance. Utilizing too little task-specific training signals causes underfitting to the ground-truth labels of downstream tasks, while the opposite causes overfitting to the ground-truth labels. To this end, we propose a novel Class-Agnostic Semi-Supervised Learning (CA-SSL) framework to achieve a more favorable task-specificity balance in extracting training signals from unlabeled data. CA-SSL has three training stages that act on either ground-truth labels (labeled data) or pseudo labels (unlabeled data). This decoupling strategy avoids the complicated scheme in traditional SSL methods that balances the contributions from both data types. Especially, we introduce a warmup training stage to achieve a more optimal balance in task specificity by ignoring class information in the pseudo labels, while preserving localization training signals. As a result, our warmup model can better avoid underfitting/overfitting when fine-tuned on the ground-truth labels in detection and segmentation tasks. Using 3.6M unlabeled data, we achieve a significant performance gain of 4.7% over ImageNet-pretrained baseline on FCOS object detection. In addition, our warmup model demonstrates excellent transferability to other detection and segmentation frameworks.Comment: Appeared in ECCV202

Lewis acid-catalyzed reactions of alcohol pro-electrophiles as novel strategies for C-C and C-N bond formation

The work in this thesis was undertaken in Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences in Nanyang Technological University from August 2006 to June 2010 under the supervision of Asst Prof Philip Wai Hong Chan. The work of this thesis has been directed toward the establishing of new Lewis acids catalyzed reaction of alcohol pro-electrophiles as novel strategies for C-C and C-N bond formation. This thesis is divided into four parts: Part I consists of Chapter I, which give an introduction of Lewis acid catalyzed reactions of alcohol pro-electrophiles, including several type of alcohols, such as allylic alcohols, propargylic alcohols, benzylic alcohols and α-cyclopropyl alcohols. Part II is aimed at exploring new strategies for C-C bond formation employing alcohols as pro-electrophiles. Chapter II addressed the gold-catalyzed allylic alkylation of aromatic and heteroaromatic compounds with allylic alcohols. In Chapter III, a novel strategy to highly conjugated indenes involving unexpected iron(II) chloride-catalyzed dimerization of 1,1,3-trisubstituted-prop-2-yn-1-ols was described. Part III exploring new strategies for C-N bond formation employing alcohols as pro-electrophiles. Chapter IV detailed the gold-catalyzed tandem amination/ring expansion of cyclopropyl methanols with sulfonamides as an expedient route to pyrrolidines. The method was shown to be applicable to a broad range of cyclopropyl methanols and sulfonamide substrates. In Chapter V, ytterbium(III) triflate-catalyzed ring opening of substituted1-cyclopropyl-2-propyn-1-ols with sulfonamides as an efficient synthetic route to conjugated enynes is described.CHEMISTRY and BIOLOGICAL CHEMISTR

Uncertainty analysis and allocation of joint tolerances in robot manipulators based on interval analysis

Many uncertain factors influence the accuracy and repeatability of robots. These factors include manufacturing and assembly tolerances and deviations in actuators and controllers. The effects of these uncertain factors must be carefully analyzed to obtain a clear insight into the manipulator performance. In order to ensure the position and orientation accuracy of a robot end effector as well as to reduce the manufacturing cost of the robot, it is necessary to quantify the influence of the uncertain factors and optimally allocate the tolerances. This involves a study of the direct and inverse kinematics of robot end effectors in the presence of uncertain factors. This paper focuses on the optimal allocation of joint tolerances with consideration of the positional and directional errors of the robot end effector and the manufacturing cost. The interval analysis is used for predicting errors in the performance of robot manipulators. The Stanford manipulator is considered for illustration. The unknown joint variables are modeled as interval parameters due to the inherent uncertainty. The cost-tolerance model is assumed to be of an exponential form during optimization. The effects of the upper bounds on the minimum cost and relative deviations of the directional and positional errors of the end effector are also studied

Interval Approach for the Modeling of Tolerances and Clearances in Mechanism Analysis

It is important to conduct error analysis of assemblies in order to ensure that the manufactured parts satisfy the design specifications. Traditionally, mechanical tolerances and clearances are modeled as random variables and the analysis is conducted using probabilistic methods. In this work, a new approach, based on interval analysis, is presented for the modeling and analysis of tolerances and clearances. The basic procedure of interval analysis involving solution of simultaneous nonlinear equations is described. The application of the approach in the fuzzy error analysis of planar and spatial mechanisms is also outlined. The treatment of the tolerances and clearances of the mechanism as interval numbers leads to a better and a more realistic estimation of the analysis results. Numerical examples are presented to illustrate the computational procedures. The results of the interval analysis, although philosophically different, are compared with those given by the probabilistic method for comparable input data; the differences found in the two sets of results are explained in terms of the basic characteristics of the two methods. This work denotes the first application of interval methods for the modeling of tolerances and clearances and the fuzzy error analysis of mechanisms